Method of producing an improved polycarbonamide by incorporating therein a chlorohydrin ether or derivative thereof

ABSTRACT

1. A METHOD OF PRODUCING AN IMPROVED FIBER-FORMING LINEAR POLYCARBONAMIDE HAVING EXCELLENT HYDROPPHILICITY WHICH COMPRISES ADDING TO (A) AT LEAST ONE OF FIBER-FORMING LINEAR POLYCARBONAMIDE-FORMING REACTANTS SELECTED FROM THE GROUP CONSISTING OF LACTAMS, W-AMINOCARBOXYLIC ACIDS AND SALTS OF A DICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF ADIPIC ACID, SEBACIC ACIDM TEREPHTHALIC ACID AND ISOPHTHALIC ACID WITH HEXAMETHYLENEDIAMINE (B) AT LEAST ONE POLYOXYALKYLENE GLYCOL DERIVATIVE SELECTED FROM THE GROUP CONSISTING OF POLYOXYALKYLENE GLYCOL-BISCHLOROHYDRIN ETHER OF THE FORMULA   HO-CH(-CH2-CL)-CH2-(O-R)N-O-CH2-CH(-OH)-CH2-CL   POLYOXYALKYLENE GLYCOL-MONOCHLOROHYDRIN ETHERS OF THE FORMULA   R&#39;&#39;-(O-R)N-O-CH2-CH(-OH)-CH2-CL   POLYOXYALKYLENE GLYCOL-BISGLYCIDYL ETHERS OF THE FORMULA   (OXIRANYL-CH2-(O-R)N-O-)-OXIRANE   POLYOXYALKYLENE GLYCOL-MONOGLYCIDYL ETHERS OF THE FORMULA   OXIRANYL-CH2-O-(R-O)N-R&#39;&#39;   POLYOXYALKYLENE GLYCOL-BISAMINOHYDRIN ETHERS OF THE FORMULA   R&#34;-NH-(CH2)2-N(-R&#34;)-CH2-CH(-OH)-CH2-(O-R)N-O-CH2-CH(-OH)-   CH2-N(-R&#34;)-(CH2)2-NH-R&#34;   AND POLYOXYALKYLENE GLYCOL-MONOAMINOHYDRIN ETHERS OF THE FORMULA   R&#39;&#39;-(O-R)N-O-CH2-CH(-OH)-CH2-N(-R&#34;)-(CH2)2-NH-R&#34;   WHREIN R IS ETHYLENE OR PROPYLENE, R&#39;&#39; IS HYDROGEN, METHYL, ETHYL, PROPYL, METHYLPHENYL OR ETHYLPHENYL, R&#34; IS HYDROGEN OR MTHYL AND N IS AN INTEGER FROM 4 TO 454, THE AMOUNT OF COMPONENT (B) BEING FROM 0.5% TO 20% BY WEIGHT OF COMPONENT (A) EITHER BEFORE, DURING OR AFTER POLYCONDENSATION OF SAID FIBER-FORMING LINEAR OLYCARBONAMIDE-FORMING REACTANTS AND THEN REACTING THE COMPONENT (A) WITH THE COMPONENTS (B) AT A TEMPERATURE OF 200-280* C. FOR AT LEAST 5 MINUTES.

United States Patent A US. Cl. 260-78 R 5 Claims ABSTRACT OF THE DISCLOSURE An improved polycarbonamide having excellent hydrophilicity is prepared by incorporating a bischlorohydrin ether or monochlorohydrin ether of polyoxyalkylene glycol or polyoxyalkylene monool, or the derivatives of said bischlorohydrin ether or monochlorohydrin ether in the polycarbonamide. The polycarbonamide of the invention is useful as a synthetic fiber.

This application is a continuation-in-part of the copending application Ser. No. 120,313, filed Mar. 2, 1971, now abandoned, which is a continuation-in-part of the parent application Ser. No. 777,864, filed Nov. 21, 1968 which is abandoned.

The present invention relates to a method of producing an improved polycarbonamide having an everlasting hydrophilicity.

Thermoplastic synthetic polymer fibers, particularly, polycarbonamide and polyester fibers which are produced in the largest amount, are extremely hydrophobic fibers as compared with natural fibers and therefore, although they develop many characteristics, this property is a great defect. Namely, the hydrophobic fibers give waxy touch, present difficulty in skin fitting applications, and are liable to cause oily stain, which is not easily removed. Furthermore, these fibers are liable to cause static electricity when rubbing, whereby these fibers absorb dusts and give various unpleasant feelings. These defects relate closely to the hydrophobicity of the fibers.

Hitherto, the term hydrophilicity has been used widely and includes sweat absorbing property, hygroscopicity and water absorbing property. In the present application, the sweat absorbing property of fibers means a water absorbing velocity when water is dropped on a woven fabric or water absorbing velocity when an end of the woven fabric is immersed into water, the hydroscopicity means percentage of an equilibrium water content at 65% RH and the water absorbing property means water absorbing percentage when fibers are immersed in water. Moreover, it is well known that the hydrophilicity is closely related with an antistaticity; that is, the higher the hydrophilicity, the larger the antistaticity.

A number of processes for improving hydrophilicity of synthetic fibers have been hitherto proposed, but a major part of them relates to sweat absorbing property and there have been few processes for improving the hygroscopicity and water absorbing property permanently. A major part of these improving processes consists in surface treatment of the synthetic fibers or the Woven fabrics thereof or a process in which an additive is mixed with polycarbonamide and incorporated in the fibers, but few methods Patented Oct. 15, 1974 have succeeded in providing those articles with such a permanent hydrophilicity that is durable for repeating washings without deteriorating various excellent physical properties inherent to the fibers.

As a method for incorporating Water absorbing substances in polycarbonamide prior to formation of filaments through spinning or molding, Japanese Pat. No. 193,864 hasdisclosed that e-caprolactam is polymerized in the presence of polyethylene glycol, but it has been difficult to polymerize polyethylene glycol with the caprolactam completely and non-reacted polyethylene glycol remains in the polycarbonamide, whereby the spinnability and drawability are badly affected and the yarn quality is deteriorated.

Furthermore, in Japanese Pat. No. 274,616, there has been disclosed a process, in which caprolactam is polymerized in the presence of an oxidized product of polyethylene glycol, but said oxide is a product obtained by treating polyethylene glycol with an oxidizing agent, so that the polyethylene glycol is considerably depolymerized and therefore, the polymerization degree of the modified polyethylene glycol is so ununiform that the regulation of viscosity of the resulting polymer during the polymerization of caprolactam can hardly be effected. In any of the above-mentioned methods, as the hygroscopicity of polycarbonamide decreases with lapse of time, the permanency of the hygroscopicity cannot be expected.

As another improving method, a process has been proposed in which a diaminized product of polyoxyethylene glycol-bischlorohydrin ether is used.

According to this process, a diaminized product of polyoxyethylene glycol-bischlorohydrin ether is reacted with a compound to obtain a water soluble compound and an aqueous solution of this compound is applied on the fibers or cloths thereof. Namely, this method is a surface treatment. Furthermore, it is difficult to produce practically this compound in a high purity and therefore, this process cannot be applied as an industrial and easy means for improving the synthetic fiber. However, the additives to be used in the present invention as illustrated hereinafter can be produced commercially and easily in a high purity.

Moreover, in US. Pat No. 2,998,295, there has been disclosed a process, in which a surface of textile material containing the CONH group is treated with a lower alkylene halogenhydrin to improve the antistaticity and in this case, it is specified that the lower alkylene halogenhydrin reacts with the CONH group in the textile material. That is, there is described in Example VI of this patent specification that the polyamide staple fibers are reacted with epichlorohydrin at 30-40 C. for minutes, whereby epichlorohydrin is reacted and bonded with the CONH group in the polyamide. It will be proved from a Compara- Example as described below that the antistaticity of the thus treated polyamide is fairly poor as compared with the case of the method of the present invention.

The inventors have made many investigations, in view of the above-described problems, in order to improve the hydrophilicity of polycarbonamide and the present invention has been accomplished.

Namely, the inventors have found that particular additives react with monomers or polymers for starting material of the fiber without inhibiting the polymerization reaction and are incorporated in the polymer homogenously, and neither cause difiicult in the subsequent spinning and drawing steps nor cause defects in the fibers and various articles formed of the fibers and can improve the hydrophilicity including sweat absorbing property, hygroscopicity and water absorbing property and further the unpleasant feeling of polycarbonamide synthetic fibers greatly.

Such particular additives are polyoxyalkylene glycol derivatives selected from the group consisting of polyoxyalkylene glycol-bischlorohydrin ethers of the formula polyoxyalkylene glycol-monochlorohydrin ethers of the formula R (OR)11 OCH2CIIOH H201, polyoxyalkylene glycol-bisglycidyl ethers of the fOrmula OHzOHCHz(OR) -OCHzCHCH polyoxyalkylene glycol-monoglycidyl ethers of the forformula polyoxyalkylene glycol-bisaminohydrin ethers of the formula and polyoxyalkylene glycol-monoaminohydrin ethers of the formula wherein R is ethylene or propylene, R is hydrogen, methyl, ethyl, propyl, phenyl, methylphenyl or ethylphenyl, R" is hydrogen or methyl and n is an integer from 4 to 454.

In the above formula, (OR) shows a homopolymer of alkylene oxide, such as ethylene oxide or propylene oxide and yet it may show random or block copolymers of ethylene oxide and propylene oxide. In this case, the molar ratio of ethylene oxide to propylene oxide can be used within the range of 100/0 40/ 60.

According to the present invention, polyoxyalkylene glycols and polyoxyalkylenemonools to be used for the production of the said polyoxyalkylene glycol derivatives include diol type polymers of polyoxyethylene glycol, polyoxypropylene glycol and random or block polymers of ethylene oxide and propylene oxide, and monool type polymers of addition products of aliphatic alcohols, such as methyl alcohol, ethyl alcohol and propyl alcohol; phenols such as phenol, methyl-phenol and ethyl-phenol with ethylene oxide or propylene oxide or the mixtures of these oxides, and polymers obtained by adding ethylene oxide with propylene oxide so as to form block segments.

In any case, the preferable average molecular weight of the polyoxyalkylene glycols or polyoxyalkylene monools ranges from 194 to 20,000, and the more preferable average molecular weight of the polyoxyalkylene glycol and monool is 600 to 10,000.

The bischlorohydrin ethers and monochlorohydrin ethers according to the present invention involve those obtained by addition reaction of the above described diol type polymers or monool type polymers with epichlorohydrin.

The derivatives of polyoxyalkylene glycol-bischlorohydrin ether and monochlorohydrin ether include his and mono-glycidyl ether, bis and mono-aminohydrin ether and in any case, mixtures of these derivatives and polyoxyalkylene glycol-bischlorohydrin ether or polyoxyalkylene glycol-monochlorohydrin ether of the starting material may be used.

As the polycarbonamides to be applied to the present invention, use may be made of homopolymers and copolymers obtained by polycondensing at least one polycarbonamide-forming compound selected from the group consisting of lactams, w-aminocarboxylic acids and salts of hexamethylenediamine with dicarboxylic acid, such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid.

The above-described polycarbonamides may be added with inorganic or organic substances, such as, delustrants, pigments, dyestuffs, light-stabilizers, heat-stabilizers, plasticizers, etc., if required. Furthermore, the polycarbonamide to which the additives are incorporated according to the present invention may be melt-blended with another thermoplastic or heat-softening polymer, such as, polycarbonamide composed of the same or different composition which contains no such additives, polyester, polyester ether, polyether, polyolcfin and the like or may be melted separately from such different polymers and then bonded thereto when forming a unitary filament by melt-spinning process.

The amount of the additives of said polyoxyalkylene glycol derivatives to be incorporated in polycarbonamide is 0.5 to 20% by weight, preferably 1 to 10% by weight based on the polycarbonamide.

If the amount of the additives is within the abovedescribed range, said additives can provide the polycarbonamide with an excellent permanent hydrophilicity without substantially deteriorating the excellent properties inherent to polycarbonamide, for example the strength and elongation, elasticity on elongation and dye-receptivity.

If said addition amount is less than 0.5% by weight,

the hydrophilicity is insufiicient, while, if said amount is more than 20% by weight, the additives act as a polymerization inhibitor and the viscosity of the polycarbonamide does not increase to such an extent that the polycarbonamide is provided with a spinnability high enough to enable it to be spun effectively and moreover excellent strength and elongation, elasticity on elongation, dyereceptivity and other preferable properties inherent to polycarbonamide are considerably deteriorated, so that such an amount is not preferable.

The above-described additives to be incorporated in polycarbonamide may be liquid, grease or aqueous solution.

The addition of the additives may be effected either into the starting materials of the polycarbonamide, during the polycondensation reaction, prior to completion of the reaction or into melted polycarbonamide after completion of the polycondensation reaction and said additives can be incorporated in the polycarbonamide uniformly.

The above-described additives have an excellent compatibility with polycarbonamide, and consequently the additives are well reacted with melted polycarbonamide in order to form an excellent copolycarbonamide. Such copolycarbonamide, directly or after molded into fine particulates or chips, can be melt-spun in a conventional process.

The time required for copolymerizing the additives with polycarbonamide is at least 5 minutes, preferably at least 10 minutes and the temperature for said copolymerization is ZOO-280 C.

If the temperature is less than 200 C., the fiber-forming linear polycarbonamide cannot be obtained, while if the temperature is more than 280 C., the polycarbonamide decomposes during the copolymerization reaction.

The polycarbonamide according to the present invention has such a permanent hydrophilicity that is not varied with lapse of time nor is decreased by washing with water, in addition to the excellent properties inherent to polycarbonamide. Further, even if fine granules or fine flakes of the polycarbonamide containing the additive or the fibers obtained by spinning the polycarbonamide or various articles produced of the fibers are washed with hot water or warm water containing a detergent repeatedly, the additives are not dissolved off. Accordingly, the defect of polycarbonamide owing to poor hydrophilicity or drawbacks of the conventional method for providing polycarbonamide with a temporary hydrophilicity can be completely obviated and particularly an unpleasant feeling inherent to synthetic fibers can be eliminated and the fiber made of the polycarbonamide processed by the present invention has similar texture to that of natural fiber and is preferable for raw materials of various cloths, interior ornaments, industrial materials, etc.

The invention will be further explained in detail by the following examples, which are not limitative within the scope of the invention.

The thus obtained dried fine chips were melt-extruded through a nozzle by means of a heat-grid type melt spinning apparatus after 40 minutes in molten state and the resulting undrawn filaments of 259 d./18 f. were wound on bobbins and then the undrawn filaments were left to stand at C. under 65/ RH for 20 hours and then cold-drawn 3.69 times their original length to obtain drawn filament having properties as shown in the following Table 1.

TABLE 1 Polymer Filament Water soluble Amount of water Amount of [1;] at compo- Elonabsorbed (percent) PE G-BCHE 30 C. in nent Stren th gation added (percent) m-eresol (percent) (g. d.) (percent) 80% RH 100% RH 1. 2 10. 7 5. 3 29. 8 5. 0 9.0 1. 3 10. 1 5. 5 28. 3 5. 1 10. 1 1. 1 10. 4 4. 9 36. 2 5. 5 13. 7 1.1 10.0 5. 2 29. 8 5. 6 14. 6 l. 0 9. 8 5.1 27. 6 5. 8 15. 8 1. 2 8. 9 5. 2 30.1 6. 0 16. 2 l. 1 10.5 5. 0 32. 0 6. 1 17. 0 0. 9 12. 6 4. 1 40. 5 6. 8 19. 4 0.9 13. 1 3. 7 .42. 8 7. 2 21. 5 0.6 15. 2 Spinning is impossible The part and mean by weight, unless they are stated otherwise.

EXAMPLE I In a vessel 400 parts of polyethylene glycol (abridged as PEG hereinafter) having an average molecular weight of 4,000 were melted at 80 C. and 2 parts of 47% boron trifiuoride etherate were added thereto. The resulting mixture was stirred and mixed thoroughly, and then added with 18.8 parts of epichlorohydrin dropwisely in 1 hour to react the mixture at the same temperature.

After the completion of dropping, the stirring was continued for 1 hour at the same temperature. Then the catalyst and unreacted components were distilled off on a boiling water-bath. The resulting PEG-bischlorohydrin ether (hereinafter abridged as PEG-BCHE) was dissolved in 2.5 times amount of methanol and the resulting solution was contacted with an OH-type anion exchange resin, AmberliteIRA-900 (made by Rohm & Haas Co., U.S.A.). After fully ion-exchanged, the solution was separated from the anion exchange resin and then methanol was distilled off. The purified PEG-BCHE contained 1.68% of chlorine.

Then predetermined amounts of the PEG-BCHE as shown in the following Table l, 100 parts of e-caprolactam, 3 parts of water and 0.3 part of titanium oxide were introduced into an autoclave and mixed therein and air in the autoclave was replaced with gaseous nitrogen and then the resulting mixture was heated at 260 for 3 hours under a pressure of 1.5 k.g/cm. showing gauge pressure hereinafter) and then at the same temperature for 2 hours under atmospheric pressure to obtain the primary polycondensate, which was subjected to polycondensation reaction at the same temperature for 5 hours under reduced pressure of 300 mm. Hg and then extruded in a string form from the bottom of the autoclave under a pressure of 3 kg./cm. under gaseous nitrogen atmosphere, which was passed through a water bath to be quenched and solidified and then the solidified string was cut into fine chips of 3 mm. X 3 mm.

Furthermore, as a control sample, fine chips were manufactured by mixing 100 parts of e-caprolactam, 3 parts of water, 0.3 part of titanium oxide and 0.18 part of acetic acid in the autoclave without adding PEG-BCHE and then treating the resulting mixture in the same manner under As seen from the above Table 1, when the amount of PEG-BCHE added is 0.5 to 20%, the polymer can be provided with hygroscopicity and still the strength and elongation are not substantially lowered and particularly, when said amount is 1 to 10%, preferable result can be obtained.

The above-mentioned drawn filaments were knitted into a tricot of half texture which was rinsed with a detergent and washed with water, and dried. Water was dropped on the horizontally stretched tricots from a height of 2 cm. and the time necessary for spreading into a circle of 4 cm. diameter was determined and such a time was adopted as sweat absorbing velocity. The result is shown in Table 2.

TABLE 2 Amount of PEG-BCHE added (percent):

Sweat absorbing velocity (sec.)

Furthermore, after the filament obtained by incorporating 5% of PEG-BCHE was boiled for 1 hour in pure Water and then dried, said filament was measured with respect to the hygroscopicity and such a measurement was repeated to obtain the following results.

TABLE 3 Repeating times of boiling 1 2 3 4 5 Amount of water absorbed at RH (percent) 16.2 16.0 16.1 15.8 15.7

As seen from the above Table 3, hydrophilicity owing to PEG-BCHE was not lost even by repeated washing with water.

EXAMPLE 2 In the same manner as described in Example 1, PEGs having different average molecular weights as shown in the following Table 4 were reacted respectively with epichlorohydrin in a molar ratio of PEG/epichlorohydrin'=1/2 in the presence of a catalyst of 47% boron trifiuoride etherate in a molar ratio of PEG-OH group/ BF =l/0.075, and the resulting PEG-BCHE was purified by ion exchange. Then 5% of each PEG-BCHE were added to e-caprolactam before the polymerization reaction under the same condition as described in Example 1 to obtain respective fine chips of polycarbonamide which was incorporated with the PEG-BCHE.

The thus obtained fine chips were subjected, in the same manner as described in Example 1, to washing with hot water, drying and melt-spinning to form filaments which were then drawn to obtain drawn filaments. Various properties were measured with respect to the drawn fila- The resulting fine chips were respectively washed with water, dried, spun by means of an extruder and cold drawn in the same manner as described in Example 1 to obtain drawn filaments. Various properties were measured with respect to the drawn filaments and the results as shown in the following Table were obtained.

ments and the results as shown in the following Table 4 Each of the above-mentioned filaments was knitted into were obtained. a tricot, and the sweat absorbing velocity was determined.

TABLE 4 Polymer Filament Water soluble Amount of water Average molec- [1;] at compo- Elongaabsorbed (percent) ular weight 111 mnent Strength tion of PE G used cresol (percent) (g./d.) (percent) 80% RH 100% RBI 1. 2 10. 7 5. 3 29. 8 5. 0 9.0 O. 8 13. 8 3. 6 46. 5 5. 2 10. 8 0. 9 12. 1 4. 5 37. 3 5. 4 l3. 9 1. O 10. 5 4. 8 32. 8 5. 8 15. 3 1. 1 9. 5 5. 0 31. 6 5. 7 15. 8 1. 2 8. 9 5. 2 30. 1 6. O 16. 2 1. 1 10. 5 5. 1 29. 6 5. 8 15. 1 1. 0 12. 8 4. 8 32. 7 5. 6 13. 8 1. 1 14. 0 5. 0 30. 2 5. 1 9. 5

1 PE G-BOHE is not added.

As seen from the above Table 4, when the average molecular weight of PEG used was ZOO-20,000, the ecaprolactam was polymerized without difiiculty, and the resulting polymer and the filament obtained therefrom had substantially the same preferable properties as those of nylon produced in a conventional manner, and moreover the filament had an excellent hygroscopicity. It was found that when the average molecular weight of PEG was 60010,000, this tendency was remarkable and the preferable result can be obtained.

Even though the thus obtained filament was washed with hot water repeatedly, the hydrophilicity was not substantially changed.

Example 3 PEG-BCHE was produced with the use of PEG having an average molecular weight of 1,000 in the same manner as described in Example 1. To a solution of 119 parts of the resulting PEG-BCI-IE in 5 times amount of benzene were added 300 parts of N-NaOH aqueous solution and the resulting mixture was stirred for 1 hour at room temperature. After being left to stand, the reaction mixture was separated into two layers. Benzene layer was taken out and benzene was distilled otf to obtain 65 parts of PEG-bis-glycidyl ether (hereinafter abridged as PEG- BGE), which had an epoxy equivalent of 1.7 meg/g.

Then 4% of thus obtained PEG-BGE was added to e-caprolactam before the polymerization reaction under the same condition as described in Example 1 to obtain fine chips consisting of polycarbonamide incorporated with the PEG-BGE.

As a control sample, e-caprolactam was polymerized with the use of 4% of PEG as such, which had an average molecular weight of 1,000 and was not changed to derivatives, underPthe same conditions as described above, and the polymerization product was formed into fine chips.

When PEG was used alone, the sweat absorbing velocity was 68 sec., but when PEG-BGE was used, the velocity was 7 sec. Furthermore, these properties were not changed even by repeated washing.

The hygroscopicity and the result shown in Table 5 show that when PEG is added as such, PEG is not substantially incorporated in polycarbonamide, and the effect is not expected, but when PEG-BGE is added, permanent hydrophilicity can be obtained.

Example 4 With the use of a random copolymer having an average molecular weight of 800 consisting of ethylene oxide and propylene oxide in a molar ratio of 70/30 (PEPG), PEPG-BGE was produced in the same manner as described in Example 3.

50 parts of the resulting PEPG-BGE was reacted with 50 parts of water and 250 parts of ethylenediamine for 5 hours under reflux.

Then water and an excess amount of ethylenediamine were distilled off to obtain PEPG-bis-aminohydrin ether (hereinafter abridged as PEPG-BAE).

Then 6% of the PEPG-BAE was added to e-caprolactam before the polymerization reaction in the same manner as described in Example 1 to obtain fine chips of polycarbonamide incorporated with the PEPG-BAE.

In the same manner as described in Example 1 the thus obtained fine chips were subjected to washing with water, drying and extrusion spinning to form undrawn filaments, which were then cold drawn to obtain drawn filaments. The properties of the drawn filaments were measured to obtain a results as shown in the following Table 6.

TABLE 6 Polymer Filament Water Amount of water Dyeing soluble absorbed (percent) atlinity [1;] at compo- Elongafor acid 80 C. in nent Stren th tlon 100% dye Additive m-cresol (percent) (g. d.) (percent) 80% RH RH (pereent)' PEPG-BAE 1. 11.2 4. 8 31. 5. 9 15. 9 98 In the control nylon filament, 45.

Even when the filaments were washed repeatedly, the As a control sample, fine chips of nylon-6 alone and above-mentioned properties were not changed. fine chips of PET were kneaded and subjected to extrusion spinning under the same conditions as described above. Example 5 Thus, according to the invention mixed filaments hav- 300 parts of nylon-66 fine chips having an intrinsic vising resiliency and improved hydrophilicity as shown in cosity 1] of 1.1 in m-cresol solution at 30 C. and havthe following Table 8 were obtained.

TABLE 8 Property of filament Hydrophilicity of filament Amount of water Sweat Elonga- Initial absorbed (percent) absorbing Strength tron modulus velocity Sample (g./d.) (percent) (g./d.) 80% RH 100% RH (sec.)

Used PE G-B GE 5 0 20. 1 38. 1 5. 6 15. 4 32 Control 5 1 18.5 41.0 4.6 7.9 w

ing terminal amino group of 45 meg/kg. were charged Even when the thus obtained nylon-6-PET mixed filainto an autoclave, interior of which was completely rement was washed repeatedly, its hydrophilicity was not placed by gaseous nitrogen and said'nylon was melted, substantially changed. while stirring at 285 C. for 3 hours. Then to the nylon-66 EXAMPLE 7 was added 5% based on nylon-66 of PEG-BGE, the PEG of which had an average molecular weight of 2,000 or To a mixed polycarbonamide raw material consisting 5% of a mixture of 20% PEGBCHE i h 80% of PEG- of 90 parts of e-caprolactam and 10 parts of hexamethyl- BGE, both PEGs of which had the same molecular weight ehe ph halate was added 10% based on the mixed with that used above. The resulting mixture was stirred Polycarbonemide 0f PEG-BCH'E Produced With the use and mixed at 290 C. for 2' hours and then extruded of P G having an average molecular Weight of 0 i from the bottom of the autoclave under a pressure of 3 the Same manner as described in EXemPIe The resultkg./cm. under gaseous nitrogen atmosphere into string, ing mixture Y P Y under the Same conditions which was formed into fine chips and washed with hot as descrlbed 1n p e 1 and the a t n product was water, dried, melt-spun and cold drawn in the same man- Washed wlth Wafer. dfled to Obtain a nylon p y ner as described in Example 1 to obtain filaments hav- Then fine P of the yl p ly and fine chips of ing properties as shown in the following Table 7. 40 PET were con ugate spun 111 a con ugate ratio (by weight) TABLE 7 Polymer, Hydrophilicity of filament water Property of filament soluble Amount of water Sweat compo- Elongaabsorbed (percent) absorbing nent Stren h tion velocity Additives (percent) (g. d.) (percent) 80% RH 100% RH (sec.)

None 0. 1 4. e 18. 9 5. 2 10. 1 s20 PE G-BGE 1. a 4. 5 20. a 6.1 16. 5 15 PEG-BCHE/PEG-B GE 1.8 4.5 21.5 5.9 15.8 21

Even when the thus obtained hydrophilic nylon-66 filaof nylon copolymer/PET=3/l and in a sheath-core type, ments and cloths produced therefrom were washed rein which PET formed an eccentrically arranged core and peatedly, the properties were not substantially changed. the nylon copolymer formed a sheath continuously sur- EXAMPLE 6 rounding the PET along the direction of the filament axis.

As a control, a nylon copolymer produced without 80 parts of fine chips of nylon-6, which were incorpousing PEG-BCHE, and PET was conjugate spun in the rated with 8% of PEG-BGE produced from PEG having same manner under the same conditions as described an average molecular Weight of 1,000 in the same manabove. Thus, according to the invention, improved filaer as described in Example 3, and 20 parts of fine chips ments having an excellent elastic recovering property and of polyethylene terephthalate (hereinafter abridged as hydrophilicity as shown in the following Table 9 were PET) were mixed thoroughly. The resulting mixture was obtained.

TABLE 9 Hydrophiliclty of filament Property of filament Amount of water Sweat Elonga- Initial absorbed (percent)' absorbing Stren h tlon modulus velocity Sample (g. d.) (percent) (g./d.) RH 100% RH (sec.)

Used PE G-BCHE 4. 8 28. 5 34. 7 5. 4 14. 1 26 Control 4. 9 25. 7 35. 3 4. 1 6. 8 w

Even when these composite filaments were washed rekneaded in an extruder having 3 screws at 290 C. and peatedly, their hydrophilicity was not deteriorate d.

immediately subjected to extrusion spinning, and the resulting filament was hot drawn through a hot pin having EXAMPLE 8 a Surface temperature of tO Obtain a mixed fi 50 parts of monochlorohydrin ether produced with the ment of nylon-6 and PET. 75 use of monoethylether of PEG (hereinafter abridged as 1 1 Et.PEG), PEG of which had an average molecular weight of 10,000, in the same manner as described in Example 1 were reacted with 50 parts of water and 200 parts of ethylenediamine for 3 hours under reflux.

12 COMPARATIVE EXAMPLE Diethylene glycol-bischlorohydrin ether (reagent A) and polyethylene glycol-bischlorohydrin ether (reagent B) were synthesized starting from diethylene glycol and poly- Then water and an excess amount of ethylenediamine etheylene l l (molecular weight: 4,000) according to were distilled off, and the reaction product was dissolved h h d d ib d i Example 1, respectively. in 300 parts of methanol and contacted with an OH-type Next, drawn filaments of nylon-6 were subjected to a anion exchange resin, Amberlite IRA-900. After complesurface treatment according to the method described in tion of ion exchange, methanol was distilled off from the Example VI of 2,998,295: i 1S 10 Parts P the separated solution to obtain purified Et.PEG-monoamidrawn filamems 0f 70 d-/18 w 1mPI'eg nat6d wlthfm nohydrin ether (hereinafter ELPEG MAE) Then, 3% aqueous solution of 20% by weight of sodium hydroxide of the above memioned Et PEG MAE was added to in a bath ratio of 1:100 at 30 C. for 5 hours, squeezed out to a squeezing ratio of 50%, and then dried under a :gprolactam gii i g g i g i i i reduced presure at 50 C. Thereafter, the thus treated a con i m z 0 a1 filaments were impregnated with a solution consisting of fine chlps of p0 year 9 Incorporate the 10 parts of either one of said reagents and 90 parts of E E" The chlps,we re washed Wlth water toluene in a bath ratio of 1:100 at 60 C. for 2 hours. sublected to extruslon SPmPmg and cold drawn to Then, the filaments were taken out from the said solution, obtain a drawn filament. Properties of the filament were h d thoroughly with ethanol and further with water, determined to obtain a result as shown in Table 10. and dried.

TABLE 10 Polymer Filament Dyeing aifinity [1 at Water Amount of water for 30 C. soluble Elongaabsorbed (percent) acid in component Strength tion dye Additive m-cresol (percent) (g./d.) (percent) 80% RH 100% RH (pereent) Et.PE G-MAE 1. 1 9. 7 5. 0 29 5.8 it s 73 1 Control nylon-6 filament has a dyeing affinity for acid dye 01457 EXAMPLE 9 On the other hand, fine chips of nylon-6 and either one 475 g. of nylon-6 fine chips having an intrinsic viscosity [1 of 1.21 in m-cresol solution at 30 C. were charged into an autoclave of 1 1. capacity equipped with a stirrer, interior of which was completely replaced by nitrogen gas, and said nylon was melted at 265 C. Then to the melted nylon-6 were added g. of PEG-BGlE obtained in Example 8 and the resulting mixture was thoroughly mixed while stirring at a rate of 90 r.p.m. to react the mixture. After the addition of PEG-BGE, the resulting polymer was taken out in a string form from the bottom of the autoclave at predetermined time intervals, which was quenched and solidified and then the soldified string was cut into fine chips of 2.2 mm 3 mm.

The melting point of said chips were measured by means of a difierential thermal analyzer and methanol soluble portion was determined by extracting the chip with methanol by means of a Soxhlets extractor for 10 hours. The obtained results are shown in the folowing Table 11.

TABLE 11 Time (min.) 3 5 10 20 60 Melting point C.) 223 221 220 219 219 212 Methanol soluble portion (percent) 4. 8 2. 1 0. 5 0. 3 0. 6 0. 9

of said reagents were thoroughly mixed in a volume ratio of 98 parts:2 parts in a rotary dryer adjusted at C., and the resulting mixture was charged into a melt extruder with orifices of 20 mm. 4: at 280 C. and then extruded therethrough at an extrusion rate of 750 m./min. to obtain undrawn filaments of 245 d./ 18 f. The residence time of the mixture in the extruder was about 15 minutes. Then the undrawn filaments were cold-drawn to 3.5 times their original length to obtain drawn filaments of 70 d./18 f. which were then washed with water and dried.

Each of said filaments after being washed with water and dried, was measured with respect to charged voltage. The measurement of charged voltage was as follows:

The each sample was left to stand at 20 C. under 65% RH for 24 hours, and a constant tension was applied thereto by means of a tension washer. Then, the sample was contacted with titanium porcelain at a rate of 100 m./min. to generate static electricity due to friction. The generated static electricity was measured in an elecrostatic induction method by means of a rotary sector system to determine the charged voltage.

Furthermore, the said filament was subjected to a washing test to measure the durability of its antistatic property. The washing condition was as follows:

The filament was washed, while stirring, with a detergent for home use at 40 C. for 30 minutes, and washed with warm water at the same temperature 3 times every ten minutes, and further washed in flow water for 30 minutes and then dried, Thereafter, the filament was measured with respect to the charged voltage.

The obtained results are shown in the following Table 12.

TABLE 12 Reaction Spinning Filament Number of washing (times) Elonga- 0 1 5 10 20 30 Spinna- Drawa- Stren th tion Reagent Procedure bility bility (gjd) (percent) Charged voltage (v.)

U.S. Pat. 2,998,295 A Surfaci treat- 4- 7 27- 1 700 1, 100 1, 300 1,500 1, 900 2, 100

men 1 )o B do 5.0 28.7 1,900 2, 100 2,300 2,500 2, 500 2, 500 Outside of present inven- A Melt mixing.-- Slightly Peon.-- 2. 5 23. 4 1, 100 1, 300 1, 500 1, 400 1, 400 1, 800

ion. poor.

Present invention B do Good Good.-. 4.8 30.1 200 200 220 Control 1 5. 2 29. 5 2, 100 2, 300 2, 500 2, 500 2, 400 2, 500

1 Control sample was drawn filaments of nylon-6 prior to the treatment with sodium hydroxide.

N9I,A=Diethylene glycol-bischlorohydrin ether derivative; B =Polyethylene glycol-bischlorohydrin ether derivative.

As seen from the above Table 12, the reagent A has an antistatic effect, but durability is poor in the surface treatment. Namely, the reagent A does not give the durable antistatic property to the filament. Furthermore, the reagent B having large molecular weight has little effect. This is considered due to the fact that the reagent B is very poor in the reactivity with nylon-6 under the surface treating condition as described above. I

In the melt mixing method, the reagent A causes nylon-6 to become a three-dimensional structure because of its strong reactivity, so that the spinnability and drawability are very poor. In fact, it was confirmed that a large amount of insoluble substance, after spun, is existent on a filter of an extruder. Furthermore, the antistatic effect of the reagent A is fairly poor.

According to the present invention, the reagent B shows a favorable reactivity and reacts remarkably and effectively with a terminal group of melted nylon-6 during the melt mixing, so that it gives an improved durable antistatic etl'ect to nylon-6.

What is claimed is:

1. A method of producing an improved fiber-forming linear polycarbonamide having excellent hydrophilicity which comprises adding to (a) at least one of fiber-forming linear polycarbonamide-forming reactants selected from the group consisting of lactams, w-aminocarboxylic acids and salts of a dicarboxylic acid selected from the group consisting of adipic acid, sebacic acid, .terephthalic acid and isophthalic acid with hexamethylenediamine (b) at least one polyoxyalkylene glycol derivative selected from the group consisting of polyoxyalkylene glycol-bischlorohydrin ethers of the formula HOCHCH2-(OR) .,O CHzCHOH CHrCl H201 polyoxyalkylene glycol-monochlorohydrin ethers of the formula polyoxyalkylene glycol-bisglycidyl ethers of the for- 1111113,

polyoxyalkylene glycol-monoglycidyl ethers of the formula polyoxyalkylene glycol-bisaminohydrin ethers of the formula and polyoxyalkylene glycol-monoaminohydrin ethers of the formula wherein R is ethylene or propylene, R is hydrogen, methyl, ethyl, propyl, phenyl, methylphenyl or ethylphenyl, R" is hydrogen or methyl and n is an integer from 4 to 454, the amount of component (b) being from 0.5% to 20% by weight of component (a) either before, during or after polycondensation of said fiber-forming linear polycarbonamide-forming reactants and then reacting the component (a) with the component (b) at a temperature of 200-280 C. for at least 5 minutes. i 2. The method as claimed in claim 1, wherein said polyoxyalkylene glycol has an average molecular weight of 194-20,000. 3

3. The method as claimed in claim 4, wherein said polyoxyalkylene glycol has an average molecular weight of 60010,000.

4. The method as claimed in claim 1, wherein an amount of said polyoxy alkylene glycol derivative added to said polycarbonamide is 1 to 10% by weight based on the polycarbonamide.

5. A fiber-forming linear polycarbonamide having excellent hydrophilicity obtained by copolymerizing (a) at least one of fiber-forming linear polycarbonamide-forming reactants selected from the group consisting of lactams, w-aminocarboxylic acids and salts of a dicarboxylic acid selected from the group consisting of adipic acid, sebacic acid, terephthalic acid and isophthalic acid with hexamethylenediamine; with (b) at least one polyoxyalkylene glycol derivative selected from the group consisting of polyoxyalkylene glycolbischlorohydrin ethers of the formula HO OHCHz-(O R),.0 CHzCHOH CHgCl CHzCl polyoxyalkylene glycol-monochlorohydrin ethers of the formula R(OR)r-OCH:CHOH

CHzCl polyoxyalkylene glycol-bisglycidyl ethers of the formula I k i CH2CHCH (OR)nOCHzCHCHz polyoxyalkylene glycol-monoglycidyl ethers of the formula R-(OR)uOCH2CHCH polyoxyalkylene glycol-bisaminohydrin ethers of the formula H0 (HEIGH -(0 R),.0 CH CHOH CHQNRKCHQMNHR CHzNR(CH2)2NHR" and polyoxyalkylene glycol-monoarninohydroin ethers of the formula R'-(0R),.-o CHzCHOH HzNRKcHzhNHR wherein R is ethylene or propylene, R is hydrogen, methyl, ethyl, propyl, phenyl, methylphenyl or ethylphenyl, R" is hydrogen or methyl and n is an integer from 4 to 454, the amount of component (b) being from 0.5% to 20% by weight of component (a).

References Cited UNITED STATES PATENTS 2,174,619 @10/ 1939 Carothers 26078 R 2,842,462 7/1958 Haas et a1 26078 SC 2,913,433 11/1959 Wittbecker 26078 R 2,974,066 3/1961 Macura et al. 26078 SC 2,998,295 8/1961 Goldann 26078 SC 3,094,511 6/1963 Hill et al. 26078 R 3,206,328 9/1965 Shaw et al. 26078 SC 3,341,343 9/1967, Beiswanger et al. 26078 SC 3,388,104 6/1968 Crovatt 26078 SC 3,405,104 10/1968 Wakeman et al. 26029.2 N 3,459,697 8/ 1969 Goldberg et al. 26078 R HAROLD D. ANDERSON, Primary Examiner US. Cl. X.R.

8115.5; 117-161 P; 161227; 26037 N, 78 A, 7 8 L, 78 S, 78 SC, 830, 857 PE, 857 PG; 264171, 211 

1. A METHOD OF PRODUCING AN IMPROVED FIBER-FORMING LINEAR POLYCARBONAMIDE HAVING EXCELLENT HYDROPPHILICITY WHICH COMPRISES ADDING TO (A) AT LEAST ONE OF FIBER-FORMING LINEAR POLYCARBONAMIDE-FORMING REACTANTS SELECTED FROM THE GROUP CONSISTING OF LACTAMS, W-AMINOCARBOXYLIC ACIDS AND SALTS OF A DICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF ADIPIC ACID, SEBACIC ACIDM TEREPHTHALIC ACID AND ISOPHTHALIC ACID WITH HEXAMETHYLENEDIAMINE (B) AT LEAST ONE POLYOXYALKYLENE GLYCOL DERIVATIVE SELECTED FROM THE GROUP CONSISTING OF POLYOXYALKYLENE GLYCOL-BISCHLOROHYDRIN ETHER OF THE FORMULA 